Vol.

05 INTERNATIONAL JOURNAL OF PHOTOENERGY 2003

Preparation of TiO2 nanoparticles by Sol-Gel route

Y. Bessekhouad, D. Robert, and J. V. Weber
Laboratoire de Chimie et applications (LCA)-Université de Metz, Rue victor Demange,
57500-St-Avold, France

Abstract. Nanosized titanium oxide (TiO2 ) powders were prepared by emulsification-gelation technology,
hydrolysis and reflux process. Starting precursor (Tetraisopropylorthotitanate Ti(OC3 H7 )4 ) was modified
by 1,4 cyclohexane diol (C6 H14 O2 ), hydrogen peroxide (H2 O2 ) and Triethanol amine (C6 H15 NO3 ). Titanium
tetrachloride was also used as precursor. The effect of methanol on ethanol solvent was also investigated.
The powders were analyzed by X-ray diffraction (XRD) and BET technique. Scanning electron microscopy
observation was used for agglomerate observations. The photoactivity of the products obtained was taken
as efficiency of Benzamide photodegradations.

1. INTRODUCTION absolute grade, purity 99.9%; n-Hexane CH3 (CH2 )4 CH3 ,

In recent years the photocatalytic decomposition of pol-
lutant in water has received much attention [1–4]. This
process is of particular interest due to its ability to use
solar energy. When TiO2 was irradiated with wavelength
greater than 390 nm, electron-hole pairs were gener-
ated. One of the major limits of using TiO2 as pho-
tocatalyst is their relatively low value of overall quan-
tum efficiencies, combined with the necessity of using
near ultraviolet radiation. Some success in enhancing
the photocatalytic activities is obtained by the prepara-
tion of TiO2 nanoparticles. The effect of crystallite size
and quantum size effect is observed in gaseous photo-
catalytic hydrogenation of acetylene with H2 O [5]. How-
ever, there are few studies on photocatalytic activity
of nanoparticle TiO2 crystallites in aqueous suspension
systems.
Several methods of TiO2 preparation have been re-
ported in literature based on the hydrolysis of acidic
solutions of Ti (IV) salts. Also, oxidations of TiCl4 on
gaseous phase [6–8] and hydrolysis of titanium alkox-
ides [9, 10] have been used to generate finely divided
with a high purity TiO2 powders.
In the present work, we have prepared different
TiO2 nanoparticles using several precursors and differ-
ent procedure preparations. The photocatalytic activ-
ity of the materials obtained was used for Benzamide
photodecompositions in aqueous solution. Benzamide
is not adsorbed on TiO2 surface and its photodegrada-
tion mechanism is well known [11]. Moreover, it can be
considered as a model pollutant.
2. EXPERIMENTAL
2.1. Reagents. The following commercial reagents
were used without any further purifications: Tetraiso-
propylorthotitanate Ti(OC3 H7 )4 (TIPT), purity 99%;
Titanium tetrachloride (TiCl4 ), purity 99.9%; Ethanol
(EtOH) absolute grade, purity 99.9%; Methanol (MeOH)
purity 99%; Hydroxypropyl cellulose P.M. 100.000
(HPC); 1,4 CycloHexane diol C6 H14 O2 (CHD), purity
99%; Triethanol amine C6 H15 NO3 (TEA), purity 99%;
Agar-Agar pure. TiO2 -P25, purity 99.8% (degussa
Corporation).
2.2. Preparation of TiO2 nanoparticles. Method 1:
TIPT and CHD were dissolved in 300 ml of absolute
EtOH with the molar ratio (1 : 1). The reaction mixture
was stirred at 80 ◦ C for 3 h. After cooling, a controlled
amount of water was added drop-wise to the solution.
Method 2: TIPT was slowly added to a basic solution
(pH∼9) of hydrogen peroxide H2 O2 (200 ml, 3.6 M) un-
der stirring at 5 ◦ C. The yellow gel observed indicates
the formation of peroxide complex of Titanium.
Method 3: This is a variation of method 2, where
the peroxide complex of Ti is substituted by a complex
obtained by dissolution of TIPT in TEA (TEA/TIPT molar
ratio: 0.5)
The initial pH of solutions obtained from the
method 1 to 3 were adjusted to 6 by NH4 OH or HNO3 ,
and then dispersed in 100 ml of hexane with the pres-
ence of surfactant (Agar-Agar) 10−2 g/ml as emulsifying
agents. After gelation, stirring was continued for 1 h.
The gel was filtered and washed subsequently by water
(500 ml) and EtOH (200 ml), dried at room temperature
for 12 h.
Method 4: In order to get nanostructured TiO2 , the
TIPT solution is dissolved in a mixture of MeOH and
EtOH with molar ratio (1 : 1 : 10) and refluxed at 60 ◦ C
for 6 h. Water is added drop wise into the hot solution
(60 ◦ C). The precipitate is isolated by filtration, washed
with hot water and organic solvents to remove the ad-
sorbed impurities, and heated at 130 ◦ C for 12 h.
Method 5: TiCl4 was added dropwise and under stir-
ring to 500 ml of water at about 0 ◦ C. The colloidal TiO2
solution was dialyzed until the pH lay between 2 and 3.
The solvent was removed by rotary evaporation.
154 Y. Bessekhouad et al.
Method 6: The present method of synthesis is an
adaptation of the method used by K. D. Kim and H. T.
Kim [12] for the preparation of TiO2 nanosized using
a two-stage mixed method. The starting solution con-
taining water 70% and alcohol 30% (MeOH and EtOH
in the ratio 1 : 10) was added dropwise to a solution
containing: TIPT + HPC + alcohol. Thereafter, the mix-
ture resulting at the first stage was agitated for 60 min
under Ar atmosphere. When the first stage reaction
(semi bath) was finished, the bath reaction (the second
stage) was started. Two solutions containing respec-
tively (water + alcohol) and (TIPT, HPC, alcohol) were
added to the solution obtained from the first stage. The
resulting mixture was vigorously stirred during 60 min.
The powders were isolated by repeated centrifugation
and dried at 70 ◦ C for 12 h.
The obtained products were treated at 550 ◦ C for 2
or 10 hours in air.
2.3. Catalyst characterization. Powder X-ray
diffraction (XRD) was used for crystal phase identi-
fication and estimation of the anatase: rutile ratio
and the crystallite size of each phase present. The
XRD intensities of anatase (101) peak and rutile (110)
were analyzed. The percentage of rutile in the sam-
ples can be estimated from the respective integrated
XRD [9]. The crystallite size can be determined from
the broading of corresponding X-ray spectral peaks
by Scherrer formula. XRD patterns were obtained at
room temperature with a diffractometer using Cu Kα
radiations. Scanning electron microscopy (SEM) obser-
vations were performed using a HITACHI S2500. The
specific surface area of TiO2 resulting from different
methods of preparations was determined by using
nitrogen adsorptions (BET method).
2.4. Photoactivity. The benzamide was used as
supplied. In each run, 500 mg of prepared TiO2
powder was added into a 1000 ml Pyrex vessel
containing 500 ml of 10 mg of benzamide solution
([Benzamide] = 20 mg/l). The mixture was sonicated
before irradiation for 5 min. The stirred suspension was
irradiated in solar box ATLAS Suntest CPS+ simulating
natural radiation. The light source was a vapour Xenon
lamp (300 nm < λ < 800 nm). The photoactivity of each
TiO2 was evaluated by the rate of benzamide disap-
pearance. For this purpose, benzamide concentrations
at different irradiation times were followed by HPLC
equipped with a C18 column after filtration (Watmann
filter, 0.45 µm). The pH of the solution was not con-
trolled. The vessel was opened to air and samples were
taken out in regular time intervals for the determina-
tion of benzamide concentration.
3. RESULTS AND DISCUSSION
From the product of the methods 1 to 3, transparent
and acceptable rigid gels were obtained in a short time
Vol. 05
(∼ 1 h) by adjusting the pH of the solution to 6. Miukami
et al. [13] observed the reaction occurring in method 1,
several trans enolizations can be envisaged between
alkoxides and cyclohexane diol resulting in the forma-
tion of different binuclear complexes. However, it is
known that Titanium alcoxides can react with cyclic
diols giving rise to liquid chelate monomers [14]. In
our experimental condition, gel formation has not been
seen, till the gellation stages.
As regards the reactions involved in the formation
of the sol by method 2, Ti (IV) in the presence of hydro-
gen peroxide gives an intense yellow color depending
on concentration solutions, characteristic of peroxo-
complexes, such as peroxytitanato ion [Ti(OH)3 O2 ]− ,
also named peroxytitanic acid. The mechanism forma-
tion of peroxytitanic is very complex and not com-
pletely known. However, F. A. Cotton et al. [15] sug-
gested, when titanium metal was used as starting
materials at pH ∼ 11 the following reaction:
Ti◦ + 3H2 O2 −→ [Ti(OH)3 O2 ]− + H2 O + H+ .
Hydrogen peroxide must be in excess to stabilize
the solution of peroxytitanic. When H2 O2 was substi-
tuted to TEA, a stable species was generated with Ti
Alcoxide [16].
On method 4 we have used a mixture solvent con-
taining methanol and ethanol to investigate the effect
of the presence of methanol on physico-chemical prop-
erties of TiO2 .
TiO2 prepared by hydrolysis of TiCl4 in aqueous
solution has been the subject of extensive works. The
size and morphology of grain was found to be depend-
ing on a few parameters such as hydrolyse tempera-
tures, [H2 O]/[Ti4+ ] ratio and thermal treatment condi-
tions [17]. When TiCl4 hydrolyses, TiO2 particles were
generated as well as H+ and Cl− ions, the process can
be described by the following reaction:
TiCl4 + 2H2 O −→ TiO2 + 4H+ + 4Cl− .
When TiCl4 was added to aqueous solutions, the
heat of exothermic reaction was observed. The precip-
itations of TiO2 occur only when pH of solutions was
higher than 2.
Method 6 depends on a few parameters such as
reactants concentration (TIPT: H2 O: MtOH), dispersion
(volume of EtOH), quantity of HPC used, temperature
of bath in both stages. All these parameters have not
been optimized. HPC was used as a dispersant to pre-
vent agglomeration during particle growth.
3.1. Characterization of prepared TiO2 materi-
als. A thermal treatment is necessary to improve
the crystallinity of amorphous compounds. When TiO2
powders are calcinated at higher temperature, crystal
structure transformations may occur. The amorphous-
anatase and anatase-rutile transitions depend strongly
Vol. 05 Preparation of TiO2 nanoparticles by Sol-Gel route 155

on the method preparations, the nature of the pre-
cursor and calcination conditions. Generally, the com-
plete transformations of amorphous to anatase has
been found to be completed between 350 ◦ C and 450 ◦ C,
the anatase-rutile transformation has been reported to
occur in different temperature ranges from 600 ◦ C to
1100 ◦ C [18].
Typically, the XRD patterns for different products
calcinated at 550 ◦ C for 10 h were found to be more
crystallizes than the same products calcinated at 550 ◦ C
for 2 h. The products calcinated at 550 ◦ C for 10 h in-
dicate different stages of crystallizations (Figure 1),
depending on the nature of the precursor and the
procedure of preparation. Furthermore, the samples
prepared from the organic precursors presented more
ability to form a high crystallinity than the samples
generated from mineral precursors such as titanium
tetrachloride and titanium peroxide in our experimen-
tal conditions. The peaks of the samples prepared by
methods 4 and 6 were weak in comparison with others
calcinated in the same conditions. This indicates a high
101
level of crystallizations. XRD analysis of the samples
prepared by method 4 (Figure 1) showed the existence
of anatase and rutile with the ratio 23% by weight of
rutile close to that observed for TiO2 P25.
The crystallite size was estimated by Scherrer for-
mula. This method is generally accepted to estimate
the mean particle size. The result is summarized in Ta-
ble 1. In all cases, the particle size doesn’t exceed 40 nm
and the smaller crystallite was obtained with method 1
(size varied between 7 and 10 nm). A higher specific
surface was also obtained by this method (44.5 m2 g−1 )
compared with other methods that can’t exceed ∼
20 m2 g−1 .
Scanning Electron Microscopy (SEM) observation
showed high homogeneity of the samples prepared by
method 1. The aggregate formed by the emulsifant-
gelation technology has an average size in the range
of 0.4 µm (Figure 2). The samples prepared by using
reflux process (method 4) revealed two types of aggre-
gates with a different average size. In the first type, the
aggregate has a spherical shape with an average diam-
eter of 1 µm and for the second one, 0.2 µm diameters
can be observed.

3.2. Photocatalytic activity. The photoactivity of

a
TiO2 was investigated using benzamide (BZ) as the
representative aromatic pollutant. In our experimental
a a condition a direct photolysis of BZ has not been ob-
aa a
served, and the photocatalytic degradation of BZ can
Method 6
be attributed to the hydroxyle radicals OH◦ . These rad-
icals are formed by the reaction between adsorbed OH−
at the TiO2 surface and the holes “h+ ” on the valence
Method 5 band. Adsorptions of BZ at the surface of each TiO2 did
not occur in all cases.
a
Maillard et al. [11] have identified several intermedi-
ates when BZ is photodegradated on aqueous solutions.
110

a aaa a In the first stage, monohydroxylation of the aromatic

1 ara a
1 ring occurs in the three positions ortho, meta, and para
Method 4
to the amide group. Furthermore, para-benzoquinone
and ortho-hydroquinone were identified and attributed
to the second stage degradation mechanisms.
In general, the photocatalytic activity of the sam-
Method 3
ples treated at 550 ◦ C for 10 h was found to be higher
than the samples treated for 2 h. This fact could be as-
sociated to the more crystalline structure observed for
Method 2 the samples calcinated for 10 h though this long treat-
ment induces the decrease of the specific area.
In our case, the more influencing parameter is the
level of crystallinity which can be concluded from the
results of photocatalytic activity. The crystallinity and
Method 1 surface area are two parameters involving on differ-
ent ways.
20 30 40 50 60 70 80 Figure 3 shows the decreasing concentration of BZ
versus irradiation time for the samples prepared by
2θ (deg.)
method 4. The effect of heat treatment can be seen, con-
Figure 1. XRD patterns of TiO2 photocatalysts treated at firming the high photoactivity concluded for the sam-
550 ◦ C for 10 h. ples treated at 550 ◦ C for 10 h. TiO2 calcinated for 2 h
156 Y. Bessekhouad et al. Vol. 05

(a) (b)

Figure 2. SEM micrograph of TiO2 agglomerate after calcinations at 550 ◦ C for 10 h resulting from: (a) Method 1
(b) Method 4.

Table 1. Physical properties of obtained TiO2 .

Thermal treatment duration Method 1 Method 2 Method 3 Method 4 Method 5 Method 6

L (nm) 7.92 19.81 13.21 19.87 — 23.23
2h
S (m2 g−1 ) 44.5 — 23.1 17.2 14.9 6.7

L (nm) 10.02 20.24 13.21 19.81 17.23 39.65

10 h
S (m2 g−1 ) 32.07 — 19.50 14.00 15.4 6.8

25 25
[BZ],[intermediate] mg l−1

20 20
[BZ] mg l−1

15 15
(a)
10 (a)
(b) 10
(c)
5 (b)
5
0
0 50 100 150 200 0
0 50 100 150 200
Time (min)
Time (min)
Figure 3. Benzamide degradations using TiO2 resulting
Figure 4. Benzamide degradations using TiO2 resulting
from method 4 preparations: (a) after 2 h at 550 ◦ C, (b)
from method 6 preparations: (a) after 2 h at 550 ◦ C, (b) af-
after 10 h at 550 ◦ C (c) intermediate concentration proce-
ter 10 h at 550 ◦ C.
dure (a).

the maximum concentrations of intermediate were ob-

present a non-conventional degradation curve. At the
beginning, the concentration of benzamide decreased
regularly with time and then stopped when ∼ 50% of BZ
was removed (after 30 min of irradiation). After 30 more
minutes, the degradation restarted. These phenomena
can be attributed to the preferential adsorption of in-
termediate products at the surface of semi-conductors
which can react preferentially to benzamide. In fact,
served when the degradation rates become close to zero
(Figure 3). This particularity can be used for selective
degradation of compounds such as 4-hydroxy benza-
mide or others in the presence of BZ using this TiO2 .
The products resulting from method 6 preparations
were found to be time treatment independent (i.e. the
same photoactivity was observed after being treated for
2 or 10 h at 550 ◦ C, Figure 4). This due to the fact that we
Vol. 05 Preparation of TiO2 nanoparticles by Sol-Gel route
have obtained in both cases a high level of crystallinity
and the same specific surface (∼ 6.8 m2 g−1 ).
The results of photoactivity of different TiO2 calci-
nated at 550 ◦ C for 10 h can be observed in Figure 5. The
products resulting from methods 2, 3 and 5 showed
a low photoactivity. Indeed, this comportment is at-
tributed to the poor crystallinity observed by X-ray anal-
ysis. The amorphous characters of compounds induces
high concentrations of defects. Each one acts as a re-
combination center when electron and hole were gen-
erated under illuminations [19].
25
20
[BZ] mg l−1
15
10
5 phase with ∼ 10 nm crystallite size, also the surface
0 area was found to be close to TiO2 -P25. High ho-
0 20 40 60 80 100 120
Time (min)
25
20
[BZ] mg l−1
15
10
5
0 For other methods of preparation, the best photoac-
0 20 40 60 80 100 120
Time (min)
Figure 5. Photocatalytic degradation of BZ using TiO2 gen-
erated from different methods and calcinated at 550 ◦ C
during 10 h.
The same photoactivity was obtained when TiO2
from methods 6 and 1 were used though both com-
pounds have different physical properties. The very low
specific surface (6.8 m2 g−1 ) is compensated by a high
level of crytallinity for method 6 products. In addition,
the interesting surface area obtained from method 1
(32.7 m2 g−1 ) confer sufficiently active surface to com-
pensate the moderate crystallinity. The very small crys-
tallite size (∼ 10 nm) implies a high number of particles,
each particle acts like nanophotochemical radical gen-
erators.
The effect of rutile—anatase distribution on pho-
tocatalytic activity of TiO2 can be observed by using
the product resulting from method 4. In fact, the best
result of photoactivity was obtained close to that ob-
served for TiO2 P25. The higher crystallinity combined
with good surface state improve the photocatalytic per-
formance. However, the surface area obtained from this
new method of preparations is low in comparison to
TiO2 -P25 (50 m2 g−1 ).
157
It should be taken into account that this new
method of preparation combining two alcohols has
not been optimized. Nevertheless, the optimization of
method 4 in progress in our laboratory shows the high
influences of precursor, methanol and water ratios.
Temperature and time of the refluxed process are un-
der investigation.
4. CONCLUSION
The research work presented in this paper leads us
to draw the following conclusions. TiO2 nanoparticles
were successfully prepared with a crystallite size be-
tween 8 nm and 40 nm. The effect of modified pre-
cursor was observed from the product prepared by
P25
Method 1
emulsification-gelation technology. In fact, by using 1,4
Method 2 cyclohexane diol as a modified precursor, the product
Method 3 calcinated for 10 h at 550 ◦ C showed a single anatase
mogeneity of aggregate was obtained from SEM ob-
servation with an average size of 0.4 µm. For the
same technique preparations, using hydrogen perox-
ide and triethanolamine as modified precursor, TiO2
P25 on nanoparticles were obtained. However, a low level of
Method 4 crystallinity was obtained from the results of XRD anal-
Method 5
ysis. Regarding the photocatalytic benzamide degrada-
Method 6
tions we have a best result, when 1,4 cyclohexane diol
was used.
tivity was obtained from the product prepared by reflux
process and heated at 550 ◦ C for 10 h. XRD analysis of
this sample showed the presence of anatase and rutile
phases close to that observed for TiO2 -P25 (23% of ru-
tile). The crystallite size of this product was found to
be less than TiO2 -P25. SEM showed two type of aggre-
gate. In the first type, the aggregate has spherical shape
with average diameter of 1 µm and for the second one,
0.2 µm diameter can be observed.
From the physico-chemical properties of prepared
materials and their efficiency of benzamide pho-
todegradation, we can conclude that the level of crys-
tallinity is a deciding factor for benzamide degradation
and there is no evidence of relations between photocat-
alytic performance and surface area.
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